Bituminous compositions



Y 1945- J. s. MILLER ETAL l $376,798

BITUMINOUS COMPOSITION Fi1ed Jan. 19, 1944 2o l- 110 Z 1L l o 10 so .40 so o m 20 so so E EN T L ABI T PER CENT METHYL ABIETATE FIG. I' I FIG. 2

PENETRATION AT 17%. (MILLIDECIMETERS) I30' I50 I 2+0 230 250 0 SOFTENING POINT, F. FIG. .3

JOHN STROTHER MILLER JOHN L. PRESENT mvswmm.

' words,'the invention makes possible the produc- Paiented May 1945 UNITED STAT nrrumsous oomosrrrons John Strother Miller, Railway, N. J., and John L. Present, Wilmington,

Del., assignors to Hercules Powder Company, Wilmington, Del., a

corporation of Delaware Application January 19, 1

7 Claims.

This invention relates to bituminous compositions and'more particularly to improved asphaltite compositions.

The asphaltites have been heretofore modified by compounding with various combinations of residual oils, vegetable oils, lubricating oils, waxes, resins, and the like torender them suitable for use in molded articles, such as battery cases, tile, insulating material, etc., in saturating andimpregnating' operations, and in paints and japans. The modifying agents, designed priniarily to lower the softening point of the asphaltites, have not been entirely satisfactory. For. example, with lowering of the softening point, the usual-modifiers also produce a serious decrease in hardness or in toughness. This decrease in hardness or toughness is often accom- M panied by a decrease in cohesion and weathering qualities and by an increase in staining tendency.

In accordance with this invention, it has been found that compositionscan be produced from the asphaltites in a manner which permits variation of the softening point while maintaining a constant degree of hardness. In other tion of compositions having different softening points for any given hardnessj, Such compositions are obtained by compounding the asphaltites with a liquid ester of a rosin acid and a pine wood resin having a substantial content of gasoline-insoluble matter.

More specifically, the invention involves blending the asphaltite, pine wood resin, and liquid rosin ester in proportions such that the liquid rosin ester is in a quantity between about 10 per cent and about 50 per cent of the sum of the three said components and the pine wood resin is in a quantity between about 10 per cent and about 35, per cent of the sum of the asphaltite and the said resin.

Having indicated the nature of the invention, the following table is given to illustrate the compositions which may be prepared. The numerical values shown are in parts by weight.

' Table Gilsonite(grade E) so 00 so as so 7 0 10 50 Pine wood resin-50% gasoline-insoluble (Belroresin) 10 10 20 30 25 35 20 30 30 Methylabietate. 70 25 70 70 i Hydrogenated methyl s ietatc..' 30 50.... Triethylene glycol abistate 20 35 55 Ethylabietsie 10 944, Serial hi0. 518,834

The ingredients of the diiferent compositions by heating and greater hardness and higher softening points than those of Examples 1, 3, and 4. The remaining examples are illustrative of compositions having intermediate hardness and softening points.

The compositions of Examples 1, 3, and 4 are suitable for saturating paper. For example, 30- pound kraft paper was passed through a molten bath of the composition shown in Example 3 at 400 F. and excess asphaltite removed by doctor rolls. Rapid impregnation of the paper occurred. The same compositionyheated to 350 F., was coated on 30-pound kraft paper by means of a roller coater to produce a film weighing 25-35 lbs./3000 sq. ft. The lower temperature and shorter time of contact insured a coating rather than complete impregnation of paper. A laminated article was prepared from the coated sheet by passing it with an uncoated sheet through heated rollers to secure the desired adhesion.

The compositions of Examples 2, 7, and 9 have a greater hardness at normal temperatures of use and are suitable for the preparation of molded articles. Compositions represented by Examples 5, 6, and 8 are satisfactory for saturating roofing material such asshingles and are also suitable for the production of laminated articles because of their good adhesive qualities.

The accompanying drawing serves to illustrate the effect of variation in composition upon the softening points and/or hardness.

Fig. 1 shows the effect of varying quantities of methyl abietate onzthe penetration values at 77 F. of different blends of gilsonite and Belro" resin. Only one curve is shown because the effect is the same for all blends containing from 10 to 35 per cent "Belro resin and to 65 per cent gilsonite. The penetration values, which are a measure of hardness, were determined according to the standard ASTM method, D5-25 g. weight for 5 seconds at 77 F.) The values shown are the depths of penetration expressed in millidecimeters, i. e., hundredths of a centimeter.

Fig. 2 shows the effect of methyl abietate on the softening points of three different blends of 1 Curve -70 parts gilsonite 'and "Belro" resin. The blends repre- 3 sented by the curves are as follows:

3 Curve A-90 parts gilsonite and parts "Belro" resin 1 Curve B-,80 parts gilsonite and parts Belro resin gilsonite and parts "Belro resin.

, Softening points were determined by the ring and 1 ball method.

1 In Fig. 3, softening points have been plotted against penetration values at 77 F. The three curves shown represent the same blends of gilby referring to Fig. 1 where it is seen that about 41 per cent by weight of methyl abietate is necessary to produce that penetration value. In a. like manner, the softening point at the same point on the curve of Figure 3 can be compared with curve C of Figure 2 and the same percentage value for methyl abietate will be obtained.

From the curves of Figure 3, it can be seen that,

for any given penetration value, different soften- I per cent based upon the weight of position. The amount used within this ran e is dependent upon the hardness desired. Quantities below 10 per cent do not have an appreciable effect on the softening point whereas quantities above 50 per cent produce undesirable degrees of softening at normal temperatures of use such as 60-90 C., i. e., penetration value at 77 F. is excessive.

As previously mentioned, the pine wood resin employed in this invention is one which contains at least 15 per cent of gasoline-insoluble material. In general, it is preferred to use a resin having at least about and up to about -'75 per cent gasoline-insolubles. The Belro resin referred to in the earlier discussion and examples is a very suitable resin obtained from the furfural 1 solvent refining of Wood rosin and contains at least 35 per pent and usually about per cent of gasoline-insoluble material. Pine wood resins substantially completely insoluble in gasoline may also be used.

The quantity of resin employed is between about 10 and 35 per cent by weight based upon the ing points can be obtained by varying the concentrations of the components of the mixture.

The ability to lower the softening point of gilsonite and other high melting asphaltites while maintaining a constant and desirable degree of hardness at ordinary temperatures of use is of importance because it makes possible efilcient saturating and coating in molten application in the preparation of saturated, coated, laminated and molded articles. At the same time, the composi- E tions are hardv at temperatures of normal use.

Any of the asphaltites, viz., gilsonite, grahamite,

and glance pitch, may be used in this invention.

They differ from the asphalts and blown asphalts and are characterized by their hardness and high melting or softening points. In general, it is preferred to use gilsonitein the practice of this in vention.

The rosin esters employed in this invention may be any of the esters of rosin acids which are liquids at, or slightly above, ordinary room temperatures, i. e., about 25 C. The esters may be I prepared-from lower aliphatic alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, hexyl alcohol, and like alcohols, higher aliphatic alcohols such as lauryl alcohol, stearyl alcohol, oleyl alcohol, etc. and rosin acids such as abietic acid, l-pimaric acid, d-pi- -maric acid, sapinic acid, and mixtures of rosin acids such as occur in wood or gum rosin, or rosin which has been subjected to treatments such as polymerization, isomerization, the Hyex" treatment (described in U. S. Patent 2,154,629 to Litt- 4 man), hydrogenation, dehydrogenation, heat treatment, and the like. Polyalkylene glycols such as triethylene glycol, tetraethylene glycol, pentaethylene glycol, trimethylene glycol, tetramethylene glycol, etc., may also be used in preparing esters for use in this invention.

The quantity of the esters, which may be employed, lies within the range of about 10 to 50 combined weight of the asphaltite and resin. Quantities of resin below 10 per cent do not have an appreciable effect on the softening point whereas quantities above35 per cent tend to increase low temperature susceptibility, i. e., cause the compositions to be brittle at temperatures of 32 F. or lower.

It will be appreciated that this invention resides" in the temarymixture and the quantities of each component may be varied within'the ranges set forth depending upon the hardness and/or softconcentrations of each component within the .specified ranges can be used to obtain additional I curves. Also other materials will give slightly difierent sets of curves. Such curves will be useful in determining the composition necessary to produce a certain hardness and softening point.

Compositions prepared in accordance with this invention have increased utility in a wide variety of applications. Lower temperatures for melting the compositions facilitate molding, coating and laminating operations. A decrease in viscosity of the molten material, which accompanies the lowering of the softening point, increases the ease of penetration when the compositions are used for impregnation. The maintenance of hardness at normal temperatures of use while lowering the softening point increases durability in use and resistance to wear as compared to the ordinary asphalts and modifiedasphaltites. The compositions also have greater adhesion qualities and lessened susceptibility to low temperature effects such as embrittlement. A further advantage of this invention is the decreased staining tendency of the asphaltite compositions as compared to asphalts and softened asphaltites.

The compositions of this invention may be used in preparing thermoplastic molded articles, such as battery cases, tile, insulation materials, and the like, paints, japans and laminated articles such as-laminated paper. They may also be used in coating surfaces such as building roofs, paper, etc., and in impregnating paper, fiber board, wood pulp, wood felt, roofing felt, felt base for flooring, glass wool, woven fabrics, and other porous objects.

the final com- I WhatweclaimanddesiretoprotectbyLetters- Patent is:

by weight the sum of the asphaltite and resin,

and the liquid ester being present in a quantity between about per cent and about 50 per cent by weight of the said mixture.

2.-A composition comprising a mixture of an asphaltite, pine wood resin characterized by a gasoline-insoluble matter content of at least 35 per cent, and a liquid ester of a rosin acid, the

said pine wood resin being present in a quantity between about 10 per cent and about 35 per cent by weight of the sum of the asphaltite and resin, and the liquid ester being present in a quantity between about 10 per cent and about 50 per cent by weight of the said mixture.

3. A compositioncomprising a mixture of gilsonite, pine wood resin characterized by a'gasoline-insoluble matter content of at least 15 per cent, and a liquid ester of a rosin acid, the said pine wood resin being present in a quantity between about 10 per cent and about '35 percent by weight of the sum of the gilsonite and resin, and the liquid ester being present in a quantity between about 10 per cent and about 50 per cent by weight of the said mixture. 4. A composition comprising a mixture of gilsonite, pine wood resin characterized by a gasoline-insoluble matter content of at least 15 per cent, and methyl abietate, the said pine wood resin being present in a quantity between about 10 per cent and about 35 per cent by weight of the sum of the gilsonite and resin, and the methyl abietate being present in a quantity between about 10 per cent and about per cent by weight of the said mixture.

\ 5.. A composition comprising a mixture or gilsonite, pine wood resin characterized by a gasoline-insoluble matter content of at least 15 per cent, and hydrogenated methyl abietate, the said pine wood resin being present in a quantity between about 10 per cent and about 35 percent by weight of the sum of the gilsonite and resin, and the hydrogenated methyl abietate being presend in a quantity between about 10 per cent and about 50 per cent by weight of the said mixture.'

6. A composition comprising a mixture of gilsonite, pine wood resin characterized by a gasoline-insoluble matter content oi! at least 35 per "cent, and a liquid ester of a resin acid, the said pine wood resin being present in a quantity between about 10 per cent and about 35 per cent by weight of the sum of the gilsonite and resin, and the liquid ester being present in a quantity between about 10 per cent and about 50 per cent by weight of the said mixture.

line-insoluble matter content of at least 35 per cent, and methyl abietate, the said pine wood resin being present in a quantity between about 10 per cent and about 35 per cent by weight of the sum of the gilsonite and resin, and the methyl abietate beins Present in a quantity between about 10 per cent and about 50 per cent by weight of the said mixture.

- JOHN BTROTHER MILLER.

JOHN L. PRESENT. 

